ABSTRACT:Control of micellar size and cmc was studied for nonamphiphilic poly(vinyl phenol)-block-polystyrene diblock copolymers (PVPh-b-PSt) in the micellization by 1,4-butanediamine (BDA). The micellization was explored for the copolymers with Mn(PSt blocks) = 20 K, 35 K, 75 K, and 125 K, holding the PVPh block length constant (Mn(PVPh blocks) = 10 K), in order to investigate effect of the PSt block length on the size of micelles. Dynamic light scattering demonstrated that the copolymers with longer PSt blocks formed larger micelles, although the copolymers had a slight difference in the unimer size. The copolymers had the transition from the unimers to the micelles at the same BDA concentration, indicating that the cmc of the copolymers was independent of the PSt block length. The PVPh block length had effects not only on the micellar size but also on the cmc. The copolymers with longer PVPh blocks showed the transition at lower BDA concentration. When the copolymers had almost the same unit ratios of VPh to St, the copolymer with larger molecular weight formed larger micelles at lower BDA concentration. The size of micelles and the cmc were also manipulated by the mixed ratio of the copolymers with different block length.KEY WORDS Poly(vinyl phenol)-block-Polystyrene (PVPh-b-PSt) / Nonamphiphilic Diblock Copolymers / Micelles / Unimers / Hydrodynamic Radius / Critical Micelle Concentration / Block Length / Surfactants are of great importance in various fields of coloring, 1, 2 coating, 3-5 adhesion, 6, 7 water purification, 8 paper manufacturing, 9, 10 food processing, 11 and drug delivery. 12, 13 Polymeric and oligomeric surfactants are superior to monomeric surfactants in forming large size of aggregates 14,15 and in stabilizing the shapes against changes in the circumstances. 16,17 The polymeric surfactants have such benign nature environmentally so that those have been utilized as foodadditives, 18, 19 dispersing agents for cosmetics, 20, 21 and drug carriers. 22,23 The surfactants are usually amphiphilic copolymers such as block, graft, and random copolymers. The block length of hydrophobic and hydrophilic moieties in the amphiphilic copolymers is an important factor to determine the physical properties of micelles such as the size of micelles, the critical micelle concentration, and the critical micelle temperature. 16,24 Accordingly, the block length and ratios always need to be taken into consideration in designing the amphiphilic copolymers.Recently, we have found the micelle formation from "nonamphiphilic" block copolymers consisting entirely of solvent-soluble blocks. 25 The copolymers themselves show no self-assembly into micelles, however, those form micelles through aggregation of part of the structures by interacting with additives. The nonamphiphilic copolymers should create micelles in a great variety because the molecular design of the micelles can be allowed through designing the copolymers and the additives. We attained the micelle formation for a nonamphiphilic poly(vinylphenol)-block-p...